JPS63211382A - Non-aqueous color darkening agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a color deepening agent for textile products. For more details,
This invention relates to a non-aqueous color deepening agent that improves the color development of dyed products and improves the depth and clarity of colors.

[Conventional technology and problems]

Conventionally, a major drawback of synthetic fibers, particularly polyester fibers, is that the color depth and clarity of dyed products is inferior to that of natural fibers such as wool and silk. For this reason, research has continued to improve the clarity and depth of dyed products, and several reports have been made.

Example Eva, [Dye and Medicine J Vol, 15, Nll 1
．． pp. 3-8 (1970) describes dyed cloth in water (refractive index IJ3).
), it is experimentally and theoretically explained that if the dyed cloth is treated with a resin finishing agent with a low refractive index, the same color deepening effect can be obtained as when it is wetted with water. The reason for this is said to be to lower the surface reflectance. Also, “Textile Engineering” Vol. 26, N (13,1
Page 88 (1973) Ha, in a summary of the discussion entitled "Fiber Surface and Color Development," states that color development of polyester fibers with disperse dyes reduces the reflection of the surface layer and increases the amount of light that enters the fiber, increasing color development efficiency. In order to increase the refractive index, it is effective to create a layer with an appropriate refractive index on the fiber surface.
It has been shown that by painting 4), the color becomes darker.

Various proposals have been made based on these facts. JP-A-53-111192 discloses a fibrous structure having a thin film formed from a polymer having a refractive index of 1.50 or less, and a method for manufacturing the same includes a method for producing the fiber structure in which the refractive index of the polymer is 1.50 or less.
The authors propose a method in which a 5- or less-sized hexamer is placed together with fibers in a closed container and subjected to plasma polymerization or discharge graft polymerization to form a thin film. Furthermore, Japanese Patent Application Laid-open No. 55-26232 discloses that a compound having a low refractive index of 1.45 or less is adsorbed onto the surface of a fiber structure in the form of a thin film of 0.3% to 10%, and subjected to dry heat or wet heat treatment. Discloses a method for performing this, describes scales using fluororesin, acrylic ester resin, vinyl polymer, and silicone resin whose polymer refractive index is 1.45 or less as a raw material for forming a thin film, and as a specific example thereof,
It discloses a method of forming a thin film on fibers using an emulsion and a solvent solution of a fluorine-containing compound or acrylic ester, by immersion adsorption at high temperature, or by spray coating and dry heat or wet heat treatment.

However, the method disclosed in Japanese Patent Application Laid-open No. 53-111192 is a batch production method that is inefficient, requires special equipment, and causes a lot of loss as polymerized polymer adheres to the wall of the container during monomer polymerization. It has many drawbacks such as troublesome cleaning and is unsuitable for industrial production.

Furthermore, in the method disclosed in JP-A No. 55-26232, it is necessary to heat a large amount of solution to a high temperature because uniform adsorption is impossible unless the temperature is high for the method of immersion in a large bath ratio. Although it saves energy, it has the disadvantage of high cost.On the other hand, the spray coating method requires dangerous and complicated operations, and has the fatal disadvantage of uneven coating amount, resulting in a patchy and unfinished finish.

In addition, JP-A-57-176275 discloses a darkening agent made of a polymer in which a branch segment having a blocked polyfluoroalkyl group is bonded to a trunk segment, but the polymer and solvent are special. Therefore, it has little industrial utility value.

[Means for solving problems]

The present inventors can use inexpensive non-aqueous solvents such as tetrachloroethylene and trichloroethane as solvents,
In order to find a non-aqueous color deepening agent with great industrial value,
We thoroughly researched the functions required for the dark color effect and obtained the following knowledge.

That is, the deep color effect of synthetic fibers, especially polyester fibers, is 1. It is not enough to form a coating of a low refractive index polymer; a significant darkening effect is obtained by roughening the polymer on the fiber surface. Therefore, in order to adsorb a polymer onto synthetic fibers, especially polyester fibers, and roughen the surface, it is necessary for the polymer to be insoluble in a solvent and to be stably dispersed, that is, to form a non-aqueous emulsion. A graft copolymer obtained by graft polymerizing a solvent-insoluble branch polymer to a solvent-insoluble trunk polymer is suitable.

Furthermore, even with natural fibers such as wool and silk, by adsorbing polymers on the fiber surface and roughening the surface, the depth and clarity of the color improves, similar to synthetic fibers such as polyester, and a deep color effect can be obtained. It will be done. However, even if natural fibers such as wool and silk are treated with only the graft copolymer, the adhesion is poor and a sufficient deep color effect cannot be obtained. In order to enhance the darkening effect on natural fibers such as Unobe silk, it is necessary to improve the adhesion of the graft copolymer. The present inventors completed the present invention as a result of intensive research into a color-deepening agent that can produce a darkening effect on synthetic fibers such as polyester and natural fibers such as Unobe silk.

That is, the present invention provides (a) a trunk polymer that is substantially insoluble in non-aqueous solvents and has a solubility parameter in the range of 6.5 to 10.0, and a branch polymer that is soluble in cough non-aqueous solvents. A copolymer obtained by graft polymerization, wherein the weight ratio of trunk polymer/branch polymer is 90/10 to 10/9.
0 and (b) general formula (1) [wherein R is an alkyl group having 8 to 22 carbon atoms, R2 is an alkyl group having 1 to 22 carbon atoms, a hydroxyethyl group or a hydroxypropyl group, R3+ "4 is an alkyl group having 1 to 3 carbon atoms, a hydroxyethyl group, or a hydroxypropyl group, and at least one of R3 and R is a hydroxyethyl or hydroxypropyl group. Y is an ethylene or propylene group , m is the number 0 or 1, n is O
5, and X represents an anion group of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, p-toluenesulfonic acid, or a hydroxyalkane carboxylic acid having 2 to 6 carbon atoms. ] At least one quaternary ammonium salt represented by (a) copolymer/(5) quaternary ammonium salt = 951
The object of the present invention is to provide a non-aqueous color deepening agent characterized in that the content is in a range of 5 to 20/80 (weight ratio).

The backbone polymer in the copolymer of the present invention may be substantially insoluble in the solvent, such as a copolymer of polybutadiene or one or more monomers copolymerizable with butadiene and butadiene. can be mentioned.

The branch polymer may be anything that is soluble in the solvent, and includes, for example, one type of vinyl monomer polymer or a copolymer of two or more types of vinyl monomers. More specifically, monomers copolymerizable with butadiene include acrylonitrile, acrylic esters, methacrylic esters, aromatic vinyl, and the like. In addition, examples of vinyl monomers to be graft-polymerized to the backbone polymer include styrene, α-methylstyrene, α-ethylstyrene, or their nuclear-substituted derivatives, such as aromatic vinyl monomers such as vinyltoluene, isopropenyltoluene, chlorostyrene, and styrene. , methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate,
Examples include acrylic ester monomers such as methyl acrylate, ethyl acrylate, and n-butyl acrylate.

The weight ratio of trunk polymer/branch polymer is 90/10 to 10/
90, preferably in the range of 80/20 to 20/80. The backbone polymer alone is insoluble in the solvent, and furthermore, it is not possible to uniformly disperse and stabilize the secondary coagulated polymer in the solvent during polymer purification, making it unsuitable as a dark color substitute. On the other hand, a cane polymer alone is soluble in a solvent and forms a smooth film on the fiber surface, but does not roughen the surface, so a sufficient deep color effect cannot be obtained. However, when a solvent-soluble branch polymer is graft copolymerized with a solvent-insoluble trunk polymer according to the present invention, the copolymer is insoluble in a non-aqueous solvent but stably dispersed in the solvent. It forms a non-aqueous emulsion, which forms a rough surface with fine particles of 0.2 μm or less on the fiber surface, so it exhibits an excellent color-deepening effect as a non-aqueous color-deepening agent.

When the backbone polymer of the present invention is a copolymer of butadiene and another monomer, the content of butadiene is preferably 30% by weight or more, particularly preferably 50% by weight or more. When the butadiene content is less than 30% by weight, the color deepening agent obtained by graft polymerization is difficult to form a stable non-aqueous emulsion in a solvent, and the particle size increases due to secondary aggregation, resulting in poor color deepening effect.

In the present invention, the backbone polymer to be graft-polymerized preferably forms latex, the average particle size of which is 0.2.
μ or less, preferably 0.15 μ or less. When the average particle size exceeds 0.2 μm, the stability of the resulting non-aqueous emulsion is poor and the darkening effect is small.

A crosslinking agent can be added to the color deepening agent of the present invention during polymerization of the trunk polymer or graft polymerization of the branch polymer in order to improve ironing resistance.

Examples of crosslinking agents include difunctional monomers such as divinylbenzene and dimethacrylates, such as mono-, di-, tri- or tetraethylene dimethacrylate, 1.3-butylene glycol dimethacrylate, and the like.

The copolymer of the present invention is preferably blended in the composition in an amount of 1 to 20% by weight.

In the quaternary ammonium salt represented by the general formula (1) used in the present invention, those in which the number of carbon atoms in R1 is less than 8 or more than 22 are undesirable because they cause deterioration in performance, especially antistatic effect.

Furthermore, examples of X include acid residues such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, peroxyacid or paratoluenesulfonic acid, and hydroxyalkanecarboxylic acid having 2 to 6 carbon atoms. In particular,
Preferred are acid residues of para-toluenesulfonic acid and hydroxyalkane carboxylic acids (especially glycolic acid).

Specific examples of preferred quaternary ammonium salts include stearyldimethylhydroxyethylammonium paratoluenesulfonate, palmityldimethylhydroxyethylammonium paratoluenesulfonate, stearoylaminoethyldimethylhydroxyethylammonium paratoluenesulfonate, and dilauryldihydroxyethylammonium paratoluenesulfonate. , distearyldihydroxypropylammonium para-toluenesulfonate, coconut or tallow alkyldimethylhydroxyethylammonium paratoluenesulfonate, stearyldimethylhydroxyethylammonium glycolate, stearoylaminoethyldimethylhydroxyethylammonium hydroxypropionate, balmityldimethylhydroxyethylammonium glycolate rate,
Examples include dilauryldihydroxyethylammonium glycolate, stearyltrihydroxyethylammonium glycolate, myristyldihydroxyethylhydroxypropylammonium glycolate, and the like. These quaternary ammonium salts are preferably blended in the composition in an amount of 0.5 to 30% by weight.

In the present invention, the copolymer/quaternary ammonium salt is used in a weight ratio of 9515 to 20/80.
It is best to use a ratio of 15 to 30/70. Outside this range, if the amount of quaternary ammonium salt is small, the darkening effect on natural fibers such as wool will be poor.

On the other hand, if the amount of quaternary ammonium is too large, the heat resistance (iron resistance) of the treated clothing will be poor, which is not preferable.

The non-aqueous color deepening agent of the present invention is prepared as a composition by diluting and dispersing both components (a) and (b) above in a solvent, but the solvent used is not particularly limited. For example, the following synthetic solvents, petroleum solvents, alcoholic solvents, ketone solvents, tetrahydrofuran, dioxane, etc. are used. Water can also be added as long as it can be solubilized.

The total content of components (a) and (b) in the composition is 5 to 30
Weight percent is preferred.

The non-aqueous darkening agent of the present invention may optionally include anionic or nonionic surfactants or hydrotropic agents for the purpose of improving system stability, oil agents such as silicone for the purpose of improving iron slipperiness, etc. Furthermore, fragrances, dyes, pigments, fluorescent dyes, antibacterial agents, preservatives, etc. can be added.

The non-aqueous darkening agent of the present invention is diluted and dispersed in a non-aqueous solvent in an amount of 0.05 to 5% by weight, preferably 0.3 to 2% by weight. Examples of the solvent for dilution and dispersion include nonaqueous solvents with a solubility parameter in the range of 6.5 to 10.0, such as synthetic solvents such as tetrachlorethylene, trichlorethylene, trichloroethane, trichlorotrifluoroethane, naphthene, etc. , petroleum solvents with high paraffin content can be used. Alcohol solvents such as methanol, ethanol, isobutanol, and n-butanol, ketone solvents such as methyl ethyl ketone and acetone, tetrahydrofuran, dioxane, and the like can be added as necessary.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. In addition, all parts and percentages in the examples are based on weight unless otherwise specified.

Example-1 A graft copolymer was synthesized by the following method.

A) Polymerization of backbone polymer 1,3-butadiene 75 parts styrene
25 Lauryl sulfate ester soda 3.0 Potassium persulfate 0.25 Dodecyl mercaptan 0.15 Water
150 The above formulation was polymerized at 60°C for 24 hours. The polymerization rate reached 92% or more. Thereafter, the mixture was degassed in a vacuum to obtain a stable latex. The average particle size of the latex was 0.084μ. This material is used as a trunk polymer,
Graft polymerization was carried out using inbutyl methacrylate as the branch polymer with the following formulation.

B) Graft polymerization of branch polymer Trunk polymer -
1.0 Ferrous sulfate 0. Old water 16070℃,
The latex obtained by polymerization for 6 hours was poured into methanol to coagulate and precipitate the graft copolymer, and after filtration, the filtration residue was
Washed twice with methanol and dried.

Using the obtained copolymer, the compositions shown in Table 1 were prepared, and the deep color effect was investigated as follows.

The obtained sample was dissolved in tetrachlorethylene at 1.0%.
Black polyester taffeta is added to the diluted and dispersed solution.
A black wool muslin was soaked for 1 minute and then air-dried. The dark color effect is measured using a colorimetric colorimeter (manufactured by Nihon Heavy Industries, No. 100).
1DP type) was used to determine the contrast index value. The smaller the L value, the darker the color. The results are shown in Table-1.

The color deepening agent of the present invention becomes a non-aqueous emulsion in tetrachlorethylene, has good dilution and dispersibility, and has an excellent color deepening effect with polyester wool.

Example-2 Graft copolymer core polymer (X
), the ratio of inbutyl methacrylate (Y) to 20/80
Processing and measurement were carried out under the same conditions as in Example 1, using the copolymer prepared as above, varying the blending ratio with the quaternary ammonium salt, and using various quaternary ammonium salts. The results are shown in Table-2.

Table 2 continued Book 1) ΔL = L value of untreated product - Value of treated product Book 2) Good dispersibility $3) Poor ironing resistance for wool fibers The coloring agent of the present invention is tetrachlorethylene It becomes a non-aqueous emulsion with good dilution and dispersibility, and is excellent in deep color effect as with polyester wool.

Claims (1)

[Claims] 1(a) Solubility parameter is 6.5 to 10.
A copolymer obtained by graft polymerizing a branch polymer that is soluble in a non-aqueous solvent to a trunk polymer that is substantially insoluble in a non-aqueous solvent in the range of 0, wherein the weight of the trunk polymer/branch polymer is A copolymer with a ratio of 90/10 to 10/90, and (b) General formula (1) ▲ Numerical formula, chemical formula, table, etc. ▼ (1) [In the formula, R_1 is an alkyl having 8 to 22 carbon atoms group, R_2
is an alkyl group having 1 to 22 carbon atoms, a hydroxyethyl group or a hydroxypropyl group, and R_3 and R_4 are an alkyl group having 1 to 22 carbon atoms.
3, and at least one of R_3 and R_4 is a hydroxyethyl or hydroxypropyl group. In addition, Y is an ethylene or propylene group, m is a number of 0 or 1, n is a number from 0 to 5, and X^■ is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, p-toluenesulfonic acid, or the number of carbon atoms It represents an anion group of 2 to 6 hydroxyalkane carboxylic acids. ] A non-aqueous concentrate characterized by containing at least one quaternary ammonium salt represented by (a)/(b) in a weight ratio of 95/5 to 20/80. Coloring agent. 2 The trunk polymer is polybutadiene or a copolymer of butadiene and one or more monomers copolymerizable with butadiene, and the branch polymer is a polymer of one type of vinyl monomer or a polymer of two or more types of vinyl monomers. The non-aqueous darkening agent according to claim 1, which is a copolymer. 3. The non-aqueous color deepening agent according to claim 2, wherein the butadiene content of the backbone polymer is 30% by weight or more. 4. The non-aqueous darkening agent according to any one of claims 1 to 3, wherein the average particle diameter of the backbone polymer particles is 0.2 μ or less. 5. According to any one of claims 1 to 4, the counter ion X^■ of the quaternary ammonium salt is para-toluenesulfonic acid or a hydroxyalkanecarboxylic acid anion having 2 to 6 carbon atoms. Non-aqueous darkening agent.